EP1786725A2 - Brennstoffbetriebener wasserstoffgenerator - Google Patents
Brennstoffbetriebener wasserstoffgeneratorInfo
- Publication number
- EP1786725A2 EP1786725A2 EP05856809A EP05856809A EP1786725A2 EP 1786725 A2 EP1786725 A2 EP 1786725A2 EP 05856809 A EP05856809 A EP 05856809A EP 05856809 A EP05856809 A EP 05856809A EP 1786725 A2 EP1786725 A2 EP 1786725A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- hydrogen
- fuel
- engine
- reformer
- stream
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
- C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0405—Purification by membrane separation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/042—Purification by adsorption on solids
- C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
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- C—CHEMISTRY; METALLURGY
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/047—Composition of the impurity the impurity being carbon monoxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
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- C—CHEMISTRY; METALLURGY
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0495—Composition of the impurity the impurity being water
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/066—Integration with other chemical processes with fuel cells
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
- C01B2203/0822—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel the fuel containing hydrogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
- C01B2203/0827—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel at least part of the fuel being a recycle stream
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0866—Methods of heating the process for making hydrogen or synthesis gas by combination of different heating methods
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1288—Evaporation of one or more of the different feed components
- C01B2203/1294—Evaporation by heat exchange with hot process stream
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
- H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
- H01M8/0668—Removal of carbon monoxide or carbon dioxide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S123/00—Internal-combustion engines
- Y10S123/12—Hydrogen
Definitions
- the field of invention pertains to a system that combines an IC engine with a fuel processor to achieve a system that consumes hydrocarbon fuels and generates and stores hydrogen with high efficiency and low operation cost.
- Hydrogen as a fuel has attracted increasing attention.
- thermal efficiency electric energy output /thermal energy input
- hydrogen fuel is considered zero-emission fuel since the consumption of hydrogen only yields water.
- storage and distribution of hydrogen on a large scale is capital and energy intensive, which hinders the widespread use of hydrogen fuel in the economy.
- the majority of hydrogen production is via the route of natural gas steam reforming in large scale hydrogen plants.
- Heating value is the amount of energy released when a fuel is completed combusted in a steady- flow process and the products are returned to the state of reactants.
- the heating value is called lower heating value (LHV).
- LHV is a direct indication of the energy release when a certain fuel is completely combusted.
- Hydrogen may be generated on demand using small- scale reformer systems (e.g. several hundred kilograms per day) with minimal requirements for hydrogen storage.
- the US Department of Energy (USDOE) has set a cost target for on-site hydrogen production of $ 1.50 energy cost per kilogram of hydrogen produced and stored at 2,300 psi, which is equivalent to $12.50 /million kJ or $ 11.80 /million Btu.
- a low-pressure spherical storage tank may have an operation pressure in the range of 1,700-2,300 psi.
- the maximum operation pressure for a high pressure storage vessel can reach 4,500 psi or above.
- engine efficiency engine power output/LHV of fuel input.
- a fuel processor combined with an IC engine may salvage the energy in the engine exhaust and further increase the system efficiency.
- the present invention relates to methods and systems that combine the use of a fuel processor with an IC engine to increase the efficiency and lower the energy cost of hydrogen production and storage.
- the modifications to present practice to achieve the improved process are relatively straightforward and easily implemented, and produce significant and synergistic effects when used in combination.
- a system for producing compressed hydrogen comprises a fuel reformer, the reformer reacting fuel, water and air to produce a hydrogen-containing reformate; an internal combustion (IC) engine which produces mechanical energy for the system; means for providing a purified hydrogen stream from the reformate; a compressor for compressing the purified hydrogen; and one or more connectors to provide the compressed purified hydrogen to a hydrogen storage means.
- the mechanical energy from the IC engine can advantageously be used to power the compressor which compresses the purified hydrogen.
- the mechanical energy from the IC engine can also be used to compress fuel for the fuel reformer, as well as input air for the engine.
- a hydrogen producing system in accordance with the invention comprises at least some of the following components:
- a steam reformer in which a mixture of pressurized steam and a fuel (e.g. natural gas) is reacted to produce a reformate stream, the reformate stream comprising hydrogen, carbon monoxide, carbon dioxide, and water vapor;
- a fuel e.g. natural gas
- a hydrogen separator which separates the reformate stream to produce a high-purity hydrogen stream and a hydrogen-depleted reformate stream
- an IC engine e.g. a spark ignition engine such as an Otto cycle engine or a fuel compression ignition engine such as a Diesel engine
- a spark ignition engine such as an Otto cycle engine or a fuel compression ignition engine such as a Diesel engine
- a fuel compression ignition engine such as a Diesel engine
- a hydrogen compressor coupled with and driven by the mechanical energy of the IC engine, the hydrogen compressor pressurizing the high-purity hydrogen stream from the hydrogen separator;
- a hydrogen storage tank which stores the high purity hydrogen gas at an elevated pressure, preferably 2300 psi or a higher pressure;
- a fuel (e.g. natural gas) compressor preferably driven by the IC engine, which compresses fuel, and, after water injection into the pressurized fuel stream, sends the fuel and water mixture to the steam reformer;
- thermal reactor coupled with the steam reformer in which a portion of the hydrogen-depleted reformate stream from the hydrogen separator, mixed with high temperature engine exhaust and air, combusts;
- recuperative boiler-heat exchanger in which the high-temperature reformate stream from the steam reformer, and the high-temperature exhaust stream from the thermal reactor, transfer heat to the mixture of pressurized fuel (e.g. natural gas) and steam;
- pressurized fuel e.g. natural gas
- turbocharger coupled with the thermal reactor, which utilizes the thermal reactor exhaust stream to drive a compressor to increase the pressure of the inlet air to the engine;
- turbocharger-expander installed in the exhaust stream of the IC engine.
- the current invention utilizes the energy contained in the high temperature exhaust from the IC engine.
- a typical IC engine exhaust is vented to the atmosphere at 700 to 900 deg. C.
- the engine exhaust in this invention after passing through the thermal reactor and the recuperative boiler-heat exchanger, may have a temperature at 200 deg. C or lower. As a result, more energy is preserved within the system and system thermal efficiency is higher.
- the fuel mixture in the IC engine can comprise a hydrogen-depleted reformate stream from the hydrogen separator, which stream comprises hydrogen, carbon monoxide, carbon dioxide, and water.
- the presence of hydrogen supports flame propagation of the steam-diluted fuel-air mixture. It enables the operation of the IC engine at a higher stoichiometric ratio of working fluids(e.g;,. air, steam) to fuel; a high ratio, sometimes referred to as lean burn, is known to increase engine efficiency.
- lean burn operation the engine exhaust contains unconsumed oxygen.
- Another aspect of tin ' s mode of operation of an IC engine is that the combustion of the diluted fuel-air mixture occurs at a lower peak cycle temperature than that of a gasoline-fired or natural gas-fired IC engine, which has the effect of improving cycle efficiency as well as producing less NOx emissions.
- the engine-driven hydrogen compressor and natural gas compressor do not need to consume electricity. From the viewpoint of efficiency, this arrangement directly utilizes the mechanical energy produced in the IC engine to compress the gas streams, and therefore eliminates the energy loss in electricity production, transmission, and conversion back to mechanical energy to drive an electric motor- driven compressor. It also makes the system independent of an electricity source and thus may be distributed in regions without reliable access to electricity.
- this system may be built either as a stationary unit, or as a mobile unit on-board of a vehicle, which may be deployed to refill storage tanks on demand.
- the system will generally require some electricity for controls and the like. This can be provided in any convenient way, for example from an electric grid, or a fuel cell using the hydrogen produced, or a generator driven by the engine, or from a battery, which could be charged by any of the above, or by solar or wind power.
- the hydrogen separator in the system can utilize a pressure swing adsorption device (PSA) or a membrane separation system or other devices that separate hydrogen from a reformate stream.
- PSA pressure swing adsorption device
- a typical pressure ratio in a hydrogen separator is higher than 6 in normal operations.
- the combination of a hydrogen separator with an IC engine and a steam reforming system provide an operational flexibility unachievable otherwise. This is because the exhaust stream from the hydrogen separator can be consumed both in the IC engine and in the thermal reactor that is coupled with the steam reformer, both of which are engineered to handle diluted combustion mixtures.
- the pressure ratio in the hydrogen separator can be at a relatively lower value without negative impact on the system efficiency (i.e., since the hydrogen-depleted reformate stream from the separator can be used elsewhere in the system, it is not necessary to purify the highest possible amount of hydrogen, which is achieved only at very high pressure ratios).
- the IC engine may be used with or without a turbocharger.
- the turbocharger is preferably driven by the high-pressure (about 150 psi) and moderate temperature (about 200 deg. C) exhaust from the thermal reactor.
- the turbocharger compresses inlet air to the IC engine.
- the engine running at an elevated pressure has a higher volumetric efficiency and can produce a higher power in comparison with the same engine running at atmospheric pressure.
- a membrane separator which produces a hydrogen- depleted reformate stream at pressure
- the hydrogen depleted reformate is at a low pressure (e.g., 28 psi).
- the steam reforming reaction in the steam reformer may be operated in any fashion such that the reformer takes supplement heat from the thermal reactor and converts fuel to a hydrogen rich reformate stream.
- air may be added to the reactant mixture of fuel and steam.
- the reaction under this condition is called autothermal reforming.
- the steam may be reduced so that only fuel and air are in the reactant mixture.
- the corresponding reforming is called partial oxidation.
- the benefits of these alternative embodiments may include more complete fuel conversion in the steam reformer, less thermal load requirement from the thermal reactor, etc. However, use of air for fuel dilutes the hydrogen slightly, requiring more work in the separator for an equivalent volume of hydrogen.
- One reformer can be engineered to accomplish steam reforming, autothermal reforming, and partial oxidation at various operation conditions.
- the steam reformer is heated by combustion of an oxygen-containing gas, preferably the engine exhaust, or optionally a supplemental source of air or compressed air, with one or more of reformate, purified hydrogen, rejected hydrogen-depleted reformate, fuel, and auxiliary fuel.
- the hydrogen separator in the above-described embodiment can be replaced with a CO elimination means.
- a CO elimination means is to use a water gas shift reactor followed by a preferential oxidation reactor to reduce CO down to a low level, e.g., less than 100 ppm, so that the reformate is suitable to be used in a PEM fuel cell.
- the reformate cleaned of CO can be pressurized and stored in a storage tank.
- the function of the thermal reactor is to combust a fuel/air mixture to supply heat to the steam reformer, in order to drive the endothermic steam reforming reaction.
- the fuel in the thermal reactor may include reformate, hydrogen depleted reformate from the hydrogen separator, hydrogen, fuel and auxiliary fuel.
- the present invention also relates to a method of producing pressurized hydrogen for storage which comprises, in an internal combustion (IC) engine, combusting a fuel and an oxygen-containing gas to produce an oxygen-containing exhaust stream and mechanical energy; in a fuel reformer, reacting fuel, water, and an oxygen-containing gas to produce a hydrogen-containing reformate stream and a high-temperature reformer exhaust stream; pre-heating at least one of the fuel, water, and air inputs to the fuel reformer by heat transfer with at least one of the hydrogen- containing reformate stream and the high-temperature reformer exhaust stream; purifying the hydrogen-containing reformate stream to produce a purified hydrogen stream and a hydrogen-depleted reformate stream; providing the hydrogen-depleted reformate stream to at least one of the IC engine and the steam reformer for use as a fuel; and using mechanical energy from the IC engine to compress the purified hydrogen stream to a pressure suitable for storage. At least a portion of the mechanical energy from the IC engine is used to compress fuel to produce a pressur
- the compressed, purified hydrogen produced by the present method can then be stored in a suitable storage means, such as a storage tank or pressure vessel, as well as an enclosed metal hydride bed that reversibly absorbs hydrogen.
- the compressed hydrogen is preferably compressed to at least about 500 psi., even more preferably compressed to at least about 1000 psi., even more preferably compressed to at least about 2000 psi., and even more preferably compressed to at least about 4000 psi.
- the stored hydrogen can then be used for any suitable application, such as for use in a fuel cell power system, including a PEM-type fuel cell.
- Fig. 1 is a schematic of a hydrogen production and storage system according to one embodiment of the invention.
- Fig. 2 is a schematic of a second embodiment of a hydrogen production and storage system.
- Fig. 1 A description of preferred embodiments of the invention follows. Referring to the schematics illustration of Fig. 1, it will be more clearly understood how the combination of hydrogen generation, hydrogen separation, lean burn Otto combustion cycle, and hydrogen compression and storage synergistically work together in a system of the invention.
- the following example contains specific amounts of inputs and values of variables (temperature, pressure, etc) in order to provide an example of the efficiency improvement and energy cost saving possible with the present invention. These specific examples are not to be taken as limiting the scope of the invention.
- the system includes a natural gas (methane) compressor
- Natural gas is the only system energy input in this embodiment. (Note that while natural gas is presently the preferred embodiment, the system can utilize fuels other than natural gas, including, gasoline, alcohol, and any other forms of hydrocarbon fuels in liquid or gas form. The calculations in this example are specific for natural gas.)
- the natural gas input is 1.186 Ib mole/hr at atmospheric pressure.
- the engine driven natural gas compressor, CM consumes 1.6 kW of power to elevate the pressure of the natural gas to 150 psi.
- water is added at a steam/carbon ratio of 3 to 4 (3 to 4 moles of water per mole of carbon), equivalent to 3.5 to 4.74 Ib mole/hr.
- the mixture of natural gas and water then enters the recuperative boiler-heat exchanger (3), in which the mixture receives energy from the high- temperature reformate as well as from the exhaust from the thermal reactor through heat transfer.
- partial pressure vaporization occurs in the mixture of natural gas and water.
- water begins to vaporize at 280° F.
- An estimated 80% of the sensible heat from the reformate as well as from the thermal reactor exhaust can be transferred to the natural gas/steam mixture.
- this mixture enters the steam reformer (4) and is converted to a reformate stream comprising hydrogen, carbon monoxide, carbon dioxide, water, and about 4.4% methane on a dry basis.
- the steam reforming reaction is endothermic.
- the energy for the endothermic reaction is provided by a thermal reactor, which in this embodiment is integrated with steam reformer (4).
- the energy balance may be expressed as in the following: Material Balance (Ib mole/hr)
- the high pressure reformate at 150 psi then travels to Point 5, which in this embodiment is a PSA.
- the PSA separates hydrogen from the reformate by alternating between two basic steps.
- the reformate enters an absorbent bed which preferentially adsorbs CO, CO 2 , and H 2 O, etc. and lets hydrogen flow through and therefore produces a stream of high purity hydrogen gas.
- the adsorption step occurs at an elevated pressure.
- the adsorbent bed is depressuxized to allow CO, CO 2 , and H 2 O to desorb. Very often, a portion of the high purity hydrogen stream is sent back to the absorbent bed to purge out the desorbed gas.
- the split in the amount of hydrogen in the high purity hydrogen stream and that in the purge stream is directly related to the pressure ratio of the adsorption pressure and desorption pressure. A higher pressure ratio allows more hydrogen into the high purity hydrogen stream.
- Hydrogen depleted reformate stream Material flow (Ib mole/hr): 0.5 CO 2 + 0.5 CO + 2.3 H 2 O + 0.7 H 2 + 0.186
- the high purity hydrogen stream then is compressed from 150 psi to 4500 psi using a hydrogen compressor (CH) (7).
- the compressed hydrogen is then stored in a storage vessel, for later use in a fuel cell, for example, including a PEM-type fuel cell.
- the power needed to drive the hydrogen compressor is approximately 8.0 kW.
- the thermal input to the engine (8) in order to produce 8.0 kW power can be calculated as in the following:
- the energy production cost to produce 2.8 Ib mole/hr hydrogen and compress the hydrogen to 4500 psi based on this embodiment is approximately
- the hydrogen separator at Point 5 is a membrane separator.
- a membrane separator uses a membrane specifically permeable to hydrogen, very often made of precious metal such as palladium, to separate hydrogen from reformate.
- the driving force of the hydrogen permeation across the membrane is the partial pressure difference of hydrogen on the different sides of the membrane.
- the high-purity hydrogen stream is at a lower pressure and the hydrogen-depleted reformate stream is at a higher pressure.
- the high-purity hydrogen stream is at a lower pressure
- the exhaust of the thermal reactor of the reformer (4) may be maintained at an elevated pressure.
- This stream may then be used to drive an expander of a turbocompressor at Point 9, the system air inlet, which compresses engine inlet air for better reformer pressure balance and engine advantages.
- This expander may have a power surplus that can be used to reduce the power load of the IC engine.
- the expander and the engine driven natural gas compressor and hydrogen compressor have about the same efficiency, the addition of the expander will increase the system efficiency to the same level as in the first embodiment.
- a turbocharger could be driven directly by the engine, rather than directly by the engine's exhaust, but this would be less efficient.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Hydrogen, Water And Hydrids (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US57909704P | 2004-06-11 | 2004-06-11 | |
PCT/US2005/020590 WO2006083296A2 (en) | 2004-06-11 | 2005-06-10 | Fuel fired hydrogen generator |
Publications (1)
Publication Number | Publication Date |
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EP1786725A2 true EP1786725A2 (de) | 2007-05-23 |
Family
ID=36698742
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP05856809A Withdrawn EP1786725A2 (de) | 2004-06-11 | 2005-06-10 | Brennstoffbetriebener wasserstoffgenerator |
Country Status (4)
Country | Link |
---|---|
US (1) | US7434547B2 (de) |
EP (1) | EP1786725A2 (de) |
CA (1) | CA2575629A1 (de) |
WO (1) | WO2006083296A2 (de) |
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JP4586780B2 (ja) * | 2006-09-07 | 2010-11-24 | トヨタ自動車株式会社 | 作動ガス循環型エンジン |
JP4483901B2 (ja) * | 2007-06-29 | 2010-06-16 | 株式会社日立製作所 | エンジンシステム |
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Also Published As
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WO2006083296A3 (en) | 2007-04-26 |
US7434547B2 (en) | 2008-10-14 |
US20060037244A1 (en) | 2006-02-23 |
CA2575629A1 (en) | 2006-08-10 |
WO2006083296A2 (en) | 2006-08-10 |
WO2006083296A8 (en) | 2006-10-05 |
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